US4275241A - Process for the preparation of 3-phenoxy-benzaldehydes - Google Patents
Process for the preparation of 3-phenoxy-benzaldehydes Download PDFInfo
- Publication number
- US4275241A US4275241A US06/089,010 US8901079A US4275241A US 4275241 A US4275241 A US 4275241A US 8901079 A US8901079 A US 8901079A US 4275241 A US4275241 A US 4275241A
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- United States
- Prior art keywords
- phenoxy
- process according
- dichromate
- toluene
- sulphuric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 238000000034 method Methods 0.000 title claims abstract description 50
- MRLGCTNJRREZHZ-UHFFFAOYSA-N 3-phenoxybenzaldehyde Chemical class O=CC1=CC=CC(OC=2C=CC=CC=2)=C1 MRLGCTNJRREZHZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- UDONPJKEOAWFGI-UHFFFAOYSA-N 1-methyl-3-phenoxybenzene Chemical compound CC1=CC=CC(OC=2C=CC=CC=2)=C1 UDONPJKEOAWFGI-UHFFFAOYSA-N 0.000 claims abstract description 24
- KGANAERDZBAECK-UHFFFAOYSA-N (3-phenoxyphenyl)methanol Chemical compound OCC1=CC=CC(OC=2C=CC=CC=2)=C1 KGANAERDZBAECK-UHFFFAOYSA-N 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 17
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 17
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- -1 alkali metal dichromate Chemical class 0.000 claims description 11
- 229910052801 chlorine Chemical group 0.000 claims description 11
- 239000000460 chlorine Chemical group 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims 3
- 101150108015 STR6 gene Proteins 0.000 claims 1
- 235000019445 benzyl alcohol Nutrition 0.000 claims 1
- 238000002955 isolation Methods 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 44
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- 239000000470 constituent Substances 0.000 description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 38
- QUYVTGFWFHQVRO-UHFFFAOYSA-N 1-(chloromethyl)-3-phenoxybenzene Chemical class ClCC1=CC=CC(OC=2C=CC=CC=2)=C1 QUYVTGFWFHQVRO-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000005660 chlorination reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000002585 base Substances 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- JOVSDWRNVGOQNK-UHFFFAOYSA-N 1-(dichloromethyl)-3-phenoxybenzene Chemical compound ClC(Cl)C1=CC=CC(OC=2C=CC=CC=2)=C1 JOVSDWRNVGOQNK-UHFFFAOYSA-N 0.000 description 8
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- UFXDRIJUGWOQTP-UHFFFAOYSA-N (4-fluoro-3-phenoxyphenyl)methanol Chemical compound OCC1=CC=C(F)C(OC=2C=CC=CC=2)=C1 UFXDRIJUGWOQTP-UHFFFAOYSA-N 0.000 description 3
- ILKFYEKKPVEUOK-UHFFFAOYSA-N 1-fluoro-4-methyl-2-phenoxybenzene Chemical compound CC1=CC=C(F)C(OC=2C=CC=CC=2)=C1 ILKFYEKKPVEUOK-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 2
- JDICMOLUAHZVDS-UHFFFAOYSA-N 4-fluoro-3-phenoxybenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1OC1=CC=CC=C1 JDICMOLUAHZVDS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229910003556 H2 SO4 Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SSTNIXFHCIOCJI-UHFFFAOYSA-N 1-methyl-4-phenoxybenzene Chemical compound C1=CC(C)=CC=C1OC1=CC=CC=C1 SSTNIXFHCIOCJI-UHFFFAOYSA-N 0.000 description 1
- OVYKINNIJQLKEY-UHFFFAOYSA-N 1-phenoxy-3-(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC(OC=2C=CC=CC=2)=C1 OVYKINNIJQLKEY-UHFFFAOYSA-N 0.000 description 1
- QEDSEZOAIMHSTK-UHFFFAOYSA-N 4-(chloromethyl)-1-fluoro-2-phenoxybenzene Chemical compound FC1=CC=C(CCl)C=C1OC1=CC=CC=C1 QEDSEZOAIMHSTK-UHFFFAOYSA-N 0.000 description 1
- NJZKTQSPKJPMNT-UHFFFAOYSA-N 4-(dichloromethyl)-1-fluoro-2-phenoxybenzene Chemical compound FC1=CC=C(C(Cl)Cl)C=C1OC1=CC=CC=C1 NJZKTQSPKJPMNT-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/575—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/292—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with chromium derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Definitions
- the invention relates to a process for the preparation of 3-phenoxy-benzaldehydes from 3-phenoxy-benzyl alcohols or 3-phenoxy-benzyl chlorides.
- a process for the preparation of 3-phenoxy-benzaldehydes from 3-phenoxy-benzyl alcohols has been found which is characterised in that 3-phenoxy-benzyl alcohols of the formula ##STR2## wherein R 1 and R 2 are identical or different and represent hydrogen or halogen, are oxidized in the presence of aqueous sulphuric acid in the temperature range of 50° to 125° C. with an aqueous solution of a dichromate.
- halogen can be fluorine, chlorine, bromine or iodine and preferably fluorine or chlorine.
- the 3-phenoxy-benzyl alcohols for the process according to the invention are known and can advantageously be prepared by hydrolysis of 3-phenoxy-benzyl chlorides in the temperature range of 140° to 210° C. under pressure.
- the process according to the invention is carried out in the temperature range of 50° to 125° C. and preferably 80° to 100° C.
- the process according to the invention is generally carried out under normal pressure.
- the dichromate used for the process according to the invention is generally an alkali metal dichromate. Examples which may be mentioned are sodium dichromate and potassium dichromate. Of course, it is also possible to use mixtures of different cichromates in the process according to the invention.
- the dichromate is generally employed as a 10% by weight to saturated solution and preferably a 20 to 60% by weight aqueous solution.
- the sulphuric acid (H 2 SO 4 ) content for the process according to the invention can vary within wide limits. It is generally 2.5 to 10 mols and preferably 3 to 7 mols, based on 1 mol of the dichromate.
- aqueous sulphuric acid for the process according to the invention, in general 10 to 70% strength by weight and preferably 20 to 60% strength by weight aqueous sulphuric acid is employed.
- the process according to the invention is advantageously carried out in the presence of an inert solvent which is not soluble in water.
- solvents can be, for example, aliphatic or aromatic hydrocarbons, such as, for example, hexane, any iso-octane, benzene or any of the xylenes or mixtures thereof.
- X 1 represents hydrogen or chlorine
- R 1 and R 2 are identical or different and have the abovementioned meaning
- 3-Phenoxy-toluenes chlorinated in the side chain are in themselves known (DE-OS (German Published Specification) No. 2,704,512). They can be prepared, for example, by chlorination of the corresponding 3-phenoxy-toluenes in carbon tetrachloride in the presence of a free radical initiator or on exposure to light. With a chlorination of this type, 3-phenoxy-benzal chloride, unconverted 3-phenoxy-toluene and in some cases 3-phenoxy-benzotrichloride are also obtained in addition to the 3-phenoxybenzyl chloride.
- 3-Phenoxy-toluenes chlorinated in the side chain which are formed by discontinuing the chlorination of the side chain when a mixture which contains up to 20% by weight of 3-phenoxy-benzal chloride has formed, are preferably employed in the process according to the invention.
- Aqueous bases used for the process according to the invention are, in general, aqueous solutions and/or suspensions of alkali metal or alkaline earth metal oxides, hydroxides or carbonates.
- the following bases may be mentioned as examples: sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, calcium oxide, calcium hydroxide and calcium carbonate.
- Preferred bases for the process according to the invention are sodium hydroxide, sodium carbonate, calcium oxide and magnesium oxide.
- the alkali metal and alkaline earth metal compounds can be used on their own or as a mixture. It is also possible to start the reaction with one of these compounds and to add another compound during the course of the reaction.
- the amount of base can vary within wide limits.
- the base can be employed in an amount which is 50 to 150 mol % and preferably 75 to 120 mol % of the amount equivalent to the content of side chain chlorine in the 3-phenoxy-benzyl chloride.
- the base can be added not at the start of the hydrolysis but only at a later point during the hydrolysis.
- the base is added after 50 to 85 mol % conversion, based on the content of side chain chlorine in the 3-phenoxy-benzyl chloride.
- the hydrolysis can be carried out in several stages. Thus, for example, it is possible to discontinue the reaction after about 40 to 70% of the total conversion, to remove the aqueous phase and to bring the reaction to completion with a new aqueous phase.
- the hydrolysis according to the process of the invention is carried out in the temperature range of 140° to 210° C. and preferably of 150° to 190° C.
- the reaction according to the process of the invention has generally ended after 2 to 7 hours.
- the hydrolysis according to the process of the invention can be carried out under excess pressure, in general a pressure in the range of 2 to 100 bars and preferably of 3 to 50 bars.
- the process according to the invention is appropriately carried out in a pressure vessel, for example an autoclave.
- the process according to the invention is preferably carried out under the pressure of the reaction mixture which results in the pressure vessel at the reaction temperature chosen.
- the 3-phenoxy-toluenes chlorinated in the side chain, water and, optionally, a base are introduced into an autoclave and heated to the reaction temperature.
- the reaction product can be worked up by methods which are in themselves known. For example, the aqueous layer is separated from the organic phase and a product containing 3-phenoxy-benzyl alcohol is isolated from the organic phase.
- this product is oxidised according to the invention to the 3-phenoxy-benzaldehyde.
- the resulting 3-phenoxy-benzaldehyde can be extracted, for example by extraction, preferably with the inert, non-aqueous solvent optionally added to the reaction. After drying the extraction mixture, the 3-phenoxy-benzaldehyde is obtained by distillation. It is, of course, also possible to isolate the aldehyde via the corresponding bisulphite compound.
- 3-phenoxy-benzaldehydes can be prepared by the process according to the invention from 3-phenoxy-benzyl alcohol, with the aid of the oxidation with chromate, which is in itself known, since it is known from Houben-Weyl, Volume 7/1, page 171, (1954) that primary alcohols which also contain ether groups in their molecule are destroyed by chromate.
- 3-Phenoxy-benzaldehyde is an intermediate product for plant protection agents (Nachzin aus Chemie,technik und Laboratorium 26, 120 (1978)).
- a chlorination product of the following composition is hydrolysed:
- the content of side chain chlorine is 10.1%.
- the distillate has the following composition:
- Example 1 150 g of a chlorination product having a composition as in Example 1, 13.3 g of calcium oxide and 300 g of water are stirred for 3 hours in an autoclave at 180° C. After working up, which is carried out analogously to that in Example 1, 124.2 g of distillate are obtained.
- the resulting distillate weighs 130.5 g.
- the residue weighs 5.5 g.
- the toluene is distilled off under a waterpump vacuum and the residue is distilled under a high vacuum at 0.5 bar. This gives 430.5 g of a mixture of 3-phenoxy-benzaldehyde and 3-phenoxy-toluene which has a 3-phenoxy-benzaldehyde content, determined by gas chromatography, of 54.6%.
- 165 g of H 2 O and 132.6 g of H 2 SO 4 are initially introduced into a stirred apparatus.
- 165 g of 3-phenoxy-benzyl alcohol are emulsified in the dilute sulphuric acid, by stirring.
- the emulsion is warmed to 90° C. and at this temperature a solution of 87.8 g of Na 2 Cr 2 O 7 ⁇ H 2 O in 58.5 g of H 2 O is added dropwise in the course of 30 minutes.
- the mixture is stirred for a further 30 minutes and the reaction product is extracted from the chromate liquor using 165 g of toluene.
- the toluene is evaporated off under a waterpump vacuum and the residue is distilled under a high vacuum. This gives 132.2 g of colorless 3-phenoxy-benzaldehyde which has a purity, determined by gas chromatography, of 98.2%.
- this toluene solution is emulsified with 852 g of water and 392 g of concentrated sulphuric acid by stirring well and the emulsion is heated to the boil.
- the sump temperature is a constant 90° C.
- a solution of 260 g of sodium dichromate in 173 g of water is added dropwise in the course of 30 minutes and the mixture is stirred for a further 30 minutes.
- the aqueous chromate liquor is separated off and the toluene solution is distilled in a 60 cm laboratory packed column.
- Fraction 1 consists of 3-phenoxy-toluene and Fraction 3 contains 3-phenoxy-benzaldehyde in a purity of 98.8%.
- the distillate has the following composition:
- the distillate has the following composition:
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- Chemical & Material Sciences (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for the preparation of a-phenoxy-benzaldehyde which comprises contacting the 3-phenoxy-benzyl alcohol of the formula ##STR1## wherein R1 and R2 are identical or different and represent hydrogen or halogen with an aqueous solution of a dichromate in the presence of aqueous sulphuric acid at a temperature in the range of 50° to 125° C. The 3-phenoxy-benzaldehyde can be in a mixture of other organic compounds such as obtained by hydrolyzing a 3-phenoxy toluene chlorinated in the side chain at a temperature of 140°-210° C. under pressure.
Description
The invention relates to a process for the preparation of 3-phenoxy-benzaldehydes from 3-phenoxy-benzyl alcohols or 3-phenoxy-benzyl chlorides.
It is known from DE-OS (German Published Specification) No. 2,741,764 and from DE-OS (German Published Specification) No. 2,704,512 to react a mixture of 3-phenoxy-benzyl chloride and 3-phenoxy-benzal chloride in a first reaction stage with ammonia and formaldehyde or hexamethylenetetramine and then, in a second reaction stage, to hydrolyse the product under acid conditions to 3-phenoxy-benzaldehyde. In the second reaction stage, the reaction product from the first stage is boiled under reflux in a solution containing water, acetic acid and concentrated hydrochloric acid. Corrosion problems arise at this stage when the process is carried out industrially.
A process for the preparation of 3-phenoxy-benzaldehydes from 3-phenoxy-benzyl alcohols has been found which is characterised in that 3-phenoxy-benzyl alcohols of the formula ##STR2## wherein R1 and R2 are identical or different and represent hydrogen or halogen, are oxidized in the presence of aqueous sulphuric acid in the temperature range of 50° to 125° C. with an aqueous solution of a dichromate.
The process according to the invention can be illustrated using the following reaction equation as an example: ##STR3##
For the process according to the invention, halogen can be fluorine, chlorine, bromine or iodine and preferably fluorine or chlorine.
The 3-phenoxy-benzyl alcohols for the process according to the invention are known and can advantageously be prepared by hydrolysis of 3-phenoxy-benzyl chlorides in the temperature range of 140° to 210° C. under pressure.
The process according to the invention is carried out in the temperature range of 50° to 125° C. and preferably 80° to 100° C. The process according to the invention is generally carried out under normal pressure.
The dichromate used for the process according to the invention is generally an alkali metal dichromate. Examples which may be mentioned are sodium dichromate and potassium dichromate. Of course, it is also possible to use mixtures of different cichromates in the process according to the invention.
In general, 90 to 130 mols and preferably 105 to 120 mols of the dichromate, based on 1 mol of the benzyl alcohol, are employed for the process according to the invention.
For the process according to the invention, the dichromate is generally employed as a 10% by weight to saturated solution and preferably a 20 to 60% by weight aqueous solution.
The sulphuric acid (H2 SO4) content for the process according to the invention can vary within wide limits. It is generally 2.5 to 10 mols and preferably 3 to 7 mols, based on 1 mol of the dichromate.
For the process according to the invention, in general 10 to 70% strength by weight and preferably 20 to 60% strength by weight aqueous sulphuric acid is employed.
The process according to the invention is advantageously carried out in the presence of an inert solvent which is not soluble in water. Such solvents can be, for example, aliphatic or aromatic hydrocarbons, such as, for example, hexane, any iso-octane, benzene or any of the xylenes or mixtures thereof.
In a preferred embodiment of the process according to the invention, a mixture of 3-phenoxy-toluenes, chlorinated in the side chain, of the formula ##STR4## wherein
X1 represents hydrogen or chlorine and
R1 and R2 are identical or different and have the abovementioned meaning,
is hydrolysed in a first reaction stage in the temperature range of 140° to 210° C. under pressure to give a mixture containing 3-phenoxy-benzyl alcohols of the formula (I) and this mixture is then oxidized, in a second reaction stage, in the presence of aqueous sulphuric acid in the temperature range of 50° to 125° C. with an aqueous solution of a dichromate.
3-Phenoxy-toluenes chlorinated in the side chain are in themselves known (DE-OS (German Published Specification) No. 2,704,512). They can be prepared, for example, by chlorination of the corresponding 3-phenoxy-toluenes in carbon tetrachloride in the presence of a free radical initiator or on exposure to light. With a chlorination of this type, 3-phenoxy-benzal chloride, unconverted 3-phenoxy-toluene and in some cases 3-phenoxy-benzotrichloride are also obtained in addition to the 3-phenoxybenzyl chloride.
For the process according to the invention one can use these chlorination mixtures direct, without preliminary separation.
3-Phenoxy-toluenes chlorinated in the side chain which are formed by discontinuing the chlorination of the side chain when a mixture which contains up to 20% by weight of 3-phenoxy-benzal chloride has formed, are preferably employed in the process according to the invention.
The hydrolysis of 3-phenoxy-toluenes chlorinated in the side chain, which are employed according to the preferred embodiment of the process according to the invention, to the mixture containing 3-phenoxy-benzyl alcohols can be carried out in the presence of aqueous bases.
Aqueous bases used for the process according to the invention are, in general, aqueous solutions and/or suspensions of alkali metal or alkaline earth metal oxides, hydroxides or carbonates. The following bases may be mentioned as examples: sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, calcium oxide, calcium hydroxide and calcium carbonate. Preferred bases for the process according to the invention are sodium hydroxide, sodium carbonate, calcium oxide and magnesium oxide.
The alkali metal and alkaline earth metal compounds can be used on their own or as a mixture. It is also possible to start the reaction with one of these compounds and to add another compound during the course of the reaction.
For the process according to the invention, the amount of base can vary within wide limits. In general, the base can be employed in an amount which is 50 to 150 mol % and preferably 75 to 120 mol % of the amount equivalent to the content of side chain chlorine in the 3-phenoxy-benzyl chloride.
For the hydrolysis according to the process of the invention, in general a 0.5 to 10-fold and preferably a 1.5 to 4-fold amount of water, based on the chlorination product employed, is used.
In a preferred embodiment of the process according to the invention the base can be added not at the start of the hydrolysis but only at a later point during the hydrolysis. For example, the base is added after 50 to 85 mol % conversion, based on the content of side chain chlorine in the 3-phenoxy-benzyl chloride. One can also carry out the hydrolysis without the addition of a base.
The hydrolysis can be carried out in several stages. Thus, for example, it is possible to discontinue the reaction after about 40 to 70% of the total conversion, to remove the aqueous phase and to bring the reaction to completion with a new aqueous phase.
The hydrolysis according to the process of the invention is carried out in the temperature range of 140° to 210° C. and preferably of 150° to 190° C. The reaction according to the process of the invention has generally ended after 2 to 7 hours.
The hydrolysis according to the process of the invention can be carried out under excess pressure, in general a pressure in the range of 2 to 100 bars and preferably of 3 to 50 bars. The process according to the invention is appropriately carried out in a pressure vessel, for example an autoclave. The process according to the invention is preferably carried out under the pressure of the reaction mixture which results in the pressure vessel at the reaction temperature chosen.
The process according to the invention can, for example, be carried out as follows:
If appropriate, in a first reaction stage, the 3-phenoxy-toluenes chlorinated in the side chain, water and, optionally, a base are introduced into an autoclave and heated to the reaction temperature. After the reaction has ended, the reaction product can be worked up by methods which are in themselves known. For example, the aqueous layer is separated from the organic phase and a product containing 3-phenoxy-benzyl alcohol is isolated from the organic phase.
In a second reaction stage, this product is oxidised according to the invention to the 3-phenoxy-benzaldehyde.
In order to carry out the oxidation, it is possible to emulsify the 3-phenoxy-benzyl alcohol by stirring with an aqueous solution of chromate and subsequently then to add the sulphuric acid dropwise.
However, it is also possible to mix the 3-phenoxy-benzyl alcohol with the dilute sulphuric acid and then to add the aqueous solution of chromate.
After the reaction has ended, the resulting 3-phenoxy-benzaldehyde can be extracted, for example by extraction, preferably with the inert, non-aqueous solvent optionally added to the reaction. After drying the extraction mixture, the 3-phenoxy-benzaldehyde is obtained by distillation. It is, of course, also possible to isolate the aldehyde via the corresponding bisulphite compound.
It is surprising that 3-phenoxy-benzaldehydes can be prepared by the process according to the invention from 3-phenoxy-benzyl alcohol, with the aid of the oxidation with chromate, which is in itself known, since it is known from Houben-Weyl, Volume 7/1, page 171, (1954) that primary alcohols which also contain ether groups in their molecule are destroyed by chromate.
3-Phenoxy-benzaldehydes of the formula ##STR5## wherein R1 and R2 are identical or different and have the meaning indicated above, can be prepared by the process according to the invention.
The preparation of the 3-phenoxy-benzaldehydes by the process according to the invention takes place with high yields and without by-products which are difficult to work up being obtained. Advantageously, no corrosion problems arise with the reaction.
3-Phenoxy-benzaldehyde is an intermediate product for plant protection agents (Nachrichten aus Chemie, Technik und Laboratorium 26, 120 (1978)).
A chlorination product of the following composition is hydrolysed:
______________________________________
unknown constituents 1.1%
3-phenoxy-toluene 46.7%
constituents chlorinated in the nucleus
0.7%
3-phenoxy-benzyl chloride
46.9%
unknown constituents 1.0%
3-phenoxy-benzal chloride
3.6%
______________________________________
The content of side chain chlorine is 10.1%.
150 g of this chlorination mixture, 37.5 g of 50% strength sodium hydroxide solution and 285 g of water are stirred in an autoclave for 3 hours at 180° C. After cooling, the aqueous layer is separated off and the organic phase is distilled over a distillation bridge. At a boiling point1.0 up to a temperature of 190° C., 124.6 g of distillate are obtained. A residue of 10.3 g remains.
The distillate has the following composition:
______________________________________
unknown constituents 0.4%
3-phenoxy-toluene 48.9%
constituents chlorinated in the nucleus
0.6%
3-phenoxy-benzaldehyde 4.6%
unknown constituents 0.4%
3-phenoxy-benzyl chloride
0.2%
3-phenoxy-benzyl alcohol 44.9%
______________________________________
150 g of a chlorination product having a composition as in Example 1, 13.3 g of calcium oxide and 300 g of water are stirred for 3 hours in an autoclave at 180° C. After working up, which is carried out analogously to that in Example 1, 124.2 g of distillate are obtained.
A residue of 6.5 g remains.
______________________________________
Composition of the distillate:
______________________________________
unknown constituents 0.1%
3-phenoxy-toluene 51.5%
constituents chlorinated in the nucleus
0.5%
3-phenoxy-benzaldehyde 3.1%
unknown constituents 0.1%
3-phenoxy-benzyl chloride
0.1%
3-phenoxy-benzyl alcohol 44.6%
______________________________________
150 g of a chlorination mixture which has the following composition:
______________________________________
unknown constituents 2.3%
3-phenoxy-toluene 29.8%
constituents chlorinated in the nucleus
1.3%
3-phenoxy-benzyl chloride
55.1%
unknown constituents 3.0%
3-phenoxy-benzal chloride
6.5%
______________________________________
(The content of side chain chlorine is 12.0%) 10.7 g of magnesium oxide and 300 g of water are reacted, and worked up, as described in Example 1.
The resulting distillate weighs 130.5 g. The residue weighs 5.5 g.
______________________________________
Composition of the distillate:
______________________________________
unknown constituents 1.2%
3-phenoxy-toluene 44.1%
constituents chlorinated in the nucleus
1.2%
3-phenoxy-benzaldehyde 3.0%
unknown constituents 0.6%
3-phenoxy-benzyl chloride
0.1%
3-phenoxy-benzyl alcohol 49.7%
______________________________________
100 g of a chlorination mixture with the following composition:
______________________________________
unknown constituents 1.6%
p-phenoxy-toluene 19.1%
constituents chlorinated in the nucleus
1.2%
3-phenoxy-benzyl chloride
64.1%
unknown constituents 1.2%
3-phenoxy-benzal chloride
12.9%
______________________________________
(The content of side chain chlorine is 15.9%) 27.3 g of sodium carbonate and 250 g of water are stirred in an autoclave for 3 hours at 180° C. After working up as described in Example 1, 77.1 g of distillate and 6.7 g of residue are obtained.
______________________________________
Composition of the distillate:
______________________________________
unknown constituents
3-phenoxy-toluene 29.7%
constituents chlorinated in the nucleus
1.2%
3-phenoxy-benzaldehyde 11.3%
unknown constituents 0.6%
3-phenoxy-benzyl chloride
0.3%
3-phenoxy-benzyl alcohol 55.9%
______________________________________
170 g of a chlorination mixture with the following composition:
______________________________________
unknown constituents 0.7%
3-phenoxy-4-fluoro-toluene
28.9%
constituents chlorinated in the nucleus
0.3%
3-phenoxy-4-fluoro-benzyl chloride
63.3%
unknown constituents 0.5%
3-phenoxy-4-fluoro-benzal chloride
6.3%
______________________________________
(The content of side chain chlorine is 12.4%) 53 g of 50% strength sodium hydroxide solution and 310 g of water are stirred in an autoclave for 3 hours at 180° C. After cooling, the organic phase is taken up in toluene and separated from the aqueous layer. After distilling off the toluene, 149 g of a reaction product with the following composition:
______________________________________
unknown constituents 0.2%
3-phenoxy-4-fluoro-toluene
39.3%
constituents chlorinated in the nucleus
0.6%
3-phenoxy-4-fluoro-benzaldehyde
2.3%
unknown constituents 0.3%
3-phenoxy-4-fluoro-benzyl alcohol
57.3%
remain.
______________________________________
230 g of H2 O, 135.2 g of concentrated sulphuric acid and 460 g of toluene are initially introduced into a stirred apparatus. 460 g of a mixture of 3-phenoxy-benzyl alcohol and 3-phenoxy-toluene according to Example 4, which has a 3-phenoxy-benzyl alcohol content, determined by gas chromatography, of 55.9%, are added, with vigorous stirring, and the emulsion is heated to the boil (90° C.) At this temperature, a solution of 135 g of Na2 O7 ×H2 O in 92 g of H2 O is added dropwise in the course of 40 minutes, the mixture is stirred for a further 30 minutes and cooled and the toluene phase is separated from the chromate liquor. The toluene is distilled off under a waterpump vacuum and the residue is distilled under a high vacuum at 0.5 bar. This gives 430.5 g of a mixture of 3-phenoxy-benzaldehyde and 3-phenoxy-toluene which has a 3-phenoxy-benzaldehyde content, determined by gas chromatography, of 54.6%.
165 g of H2 O and 132.6 g of H2 SO4 are initially introduced into a stirred apparatus. 165 g of 3-phenoxy-benzyl alcohol are emulsified in the dilute sulphuric acid, by stirring. The emulsion is warmed to 90° C. and at this temperature a solution of 87.8 g of Na2 Cr2 O7 ×H2 O in 58.5 g of H2 O is added dropwise in the course of 30 minutes. The mixture is stirred for a further 30 minutes and the reaction product is extracted from the chromate liquor using 165 g of toluene. The toluene is evaporated off under a waterpump vacuum and the residue is distilled under a high vacuum. This gives 132.2 g of colorless 3-phenoxy-benzaldehyde which has a purity, determined by gas chromatography, of 98.2%.
294 g of a mixture of 3-phenoxy-4-fluoro-benzyl alcohol and 3-phenoxy-4-fluoro-toluene according to Example 5, which contains 57.3% of 3-phenoxy-4-fluoro-benzyl alcohol, are emulsified in a mixture of 294 g of water and 128 g of sulphuric acid, with stirring. 294 g of toluene are added and the mixture is heated to the boiling point of the water/toluene azeotrope (90°). At this temperature a solution of 86 g of Na2 Cr2 O7 ×H2 O in 57.0 g H2 O is added dropwise in the course of 30 minutes, the mixture is stirred for a further 30 minutes and cooled and the organic phase is separated from the chromate liquor. This gives 293 g of an organic phase which has a 3-phenoxy-4-fluoro-benzaldehyde content, determined by gas chromatography, of 54.8%.
960 g of a chlorination product which has the following composition:
______________________________________
unknown constituents 1.5%
3-phenoxy-toluene 30.3%
constituents chlorinated in the nucleus
0.8%
3-phenoxy-benzyl chloride
59.1%
unknown constituents 0.8%
3-phenoxy-benzal chloride
7.5%
______________________________________
307 g of 50% strength sodium hydroxide solution and 1,758 g of water are stirred in an autoclave for 3 hours at 180° C. After cooling, 852 g of toluene are added, the mixture is rendered slightly acid with sulphuric acid and the aqueous layer is separated off.
In a stirred vessel, this toluene solution is emulsified with 852 g of water and 392 g of concentrated sulphuric acid by stirring well and the emulsion is heated to the boil. The sump temperature is a constant 90° C. A solution of 260 g of sodium dichromate in 173 g of water is added dropwise in the course of 30 minutes and the mixture is stirred for a further 30 minutes. After cooling to 50° C., the aqueous chromate liquor is separated off and the toluene solution is distilled in a 60 cm laboratory packed column.
After the toluene has distilled off, the following fractions are obtained:
______________________________________
Fraction 1 boiling point.sub.12 140°-157° C.
253.6 g
Fraction 2 boiling point.sub.12 157°-176° C.
24.8 g
Fraction 3 boiling point.sub.12 176°-178° C.
378.2 g
Residue 159.6 g
______________________________________
Fraction 1 consists of 3-phenoxy-toluene and Fraction 3 contains 3-phenoxy-benzaldehyde in a purity of 98.8%.
150 g of chlorinated material which has the following composition:
______________________________________
unknown constituents 0.9%
3-phenoxy-toluene 17.9%
constituents chlorinated in the nucleus
2.1%
3-phenoxy-benzyl chloride
61.3%
unknown constituents 1.3%
3-phenoxy-benzal chloride
16.8%
unknown constituents 2.0%
______________________________________
(The content of side chain chlorine is 15.9%) and 480 g of water are stirred in an autoclave for 3 hours at 160° C. The mixture is cooled, the aqueous layer is separated off and, after adding a further 480 g of water, the organic phase is stirred for a further 3 hours at 160° C.
After separating off the aqueous layer, this gives 125 g of an organic phase which has the following composition:
______________________________________
unknown constituents: 0.8%
3-phenoxy-toluene 21.2%
constituents chlorinated in the nucleus
2.6%
3-phenoxy-benzaldehyde 12.3%
3-phenoxy-benzyl chloride
0.9%
unknown constituents 1.8%
3-phenoxy-benzyl alcohol 60.1%
unknown constituents 0.3%
______________________________________
Based on the 3-phenoxy-benzyl chloride employed, the yield of 3-phenoxy-benzyl alcohol is 89% of the theoretical conversion.
120 g of chlorinated material with a composition as in Example 6 and 360 g of water are stirred in an autoclave at 170° C. for a total of 7 hours. A 10% strength sodium hydroxide solution is pumped in in the following amounts: 66 ml after the 1st hour, 35 ml after the 2nd hour, 35 ml after the 4th hour and 30 ml after the 6th hour. After cooling, the aqueous layer is separated off and is distilled as described in Example 2. 98 g of distillate are obtained. A residue of 5 g remains.
The distillate has the following composition:
______________________________________
unknown constituents 0.9%
3-phenoxy-toluene 19.6%
constituents chlorinated in the nucleus
2.3%
3-phenoxy-benzaldehyde 14.0%
3-phenoxy-benzyl chloride
1.1%
unknown constituents 1.3%
3-phenoxy-benzyl alcohol 60.3%
unknown constituents 0.4%
______________________________________
Based on the 3-phenoxy-benzyl chloride employed, the yield of 3-phenoxy-benzyl alcohol is 86% of the theoretical conversion.
150 g of chlorinated material having a composition as in Example 6 and 300 g of water are stirred in an autoclave at 160° C. for a total of 7 hours. 20% strength sodium hydroxide solution is pumped in in the following amounts: 45 ml after the 1st hour, 24 ml after the 2nd hour and 22 ml after the 6th hour. After cooling, the aqueous layer is separated off, a further 300 g of water are added to the organic phase and the latter is stirred for a further 4 hours at 160° C. The organic phase which is separated off is distilled. 121 g of distillate are obtained. A residue of 7.3 g remains.
The distillate has the following composition:
______________________________________
unknown constituents 0.7%
3-phenoxy-toluene 21.0%
constituents chlorinated in the nucleus
2.8%
3-phenoxy-benzaldehyde 13.3%
3-phenoxy-benzyl chloride
0.3%
unknown constituents 1.6%
3-phenoxy-benzyl alcohols
59.8%
unknown constituents 0.5%
______________________________________
Based on the 3-phenoxy-benzyl chloride employed, the yield of 3-phenoxy-benzyl alcohol is 86% of the theoretical conversion.
Claims (11)
1. A process for the preparation of a 3-phenoxy-benzaldehyde which comprises contacting the 3-phenoxy-benzyl alcohol of the formula ##STR6## wherein R1 and R2 are identical or different and represent hydrogen or halogen with an aqueous solution of a dichromate in the presence of aqueous sulphuric acid at a temperature in the range of 50° to 125° C.
2. A process according to claim 1 wherein the process is carried out at a temperature in the range of 80° to 100° C.
3. A process according to claim 1 wherein the process is carried out employing 2.5 to 10 mols sulphuric acid to 1 mol of dichromate.
4. A process according to claim 1 wherein the sulphuric acid is employed as a 10 to 70 weight percent aqueous sulphuric acid.
5. A process according to claim 1 wherein the dichromate employed is an alkali metal dichromate.
6. A process according to claim 1 wherein 0.25 to 0.4 mol of dichromate are employed per mol of benzyl alcohol.
7. Process according to claim 1 wherein a 10% by weight to saturated aqueous solution of dichromate is employed.
8. A process according to claim 1 wherein the process is carried out in the presence of an inert solvent which is not soluble in water.
9. A process for the preparation of a 3-phenoxy-benzaldehyde which comprises:
(a) hydrolyzing a 3-phenoxy toluene, chlorinated in the said chain, having the formula ##STR7## wherein X1 represents hydrogen or chlorine and
R1 and R2 are identical or different and represent hydrogen or halogen by contacting the same in a first reaction stage with water at a temperature in the range of 140° to 210 ° C. under pressure; and
(b) thereafter contacting the resultant product for step (a) with an aqueous solution of a dichromate in the presence of aqueous sulphuric acid at a temperature in the range of 50° 125° C.
10. A process according to claim 9 wherein step (b) is performed without isolation of any 3-phenoxy benzyl alcohol in the reaction product of step (a).
11. A process according to claim 9 wherein the hydrolysis of 3-phenoxy toluene chlorinated in the side chain takes place in a single reaction step.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782850180 DE2850180A1 (en) | 1978-11-18 | 1978-11-18 | METHOD FOR PRODUCING 3-PHENOXY-BENZALDEHYDES |
| DE2850180 | 1978-11-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4275241A true US4275241A (en) | 1981-06-23 |
Family
ID=6055084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/089,010 Expired - Lifetime US4275241A (en) | 1978-11-18 | 1979-10-29 | Process for the preparation of 3-phenoxy-benzaldehydes |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4275241A (en) |
| EP (1) | EP0011208B1 (en) |
| JP (1) | JPS5572135A (en) |
| BR (1) | BR7907402A (en) |
| CS (1) | CS208795B2 (en) |
| DD (1) | DD147354A5 (en) |
| DE (2) | DE2850180A1 (en) |
| DK (1) | DK488179A (en) |
| IL (1) | IL58732A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4365072A (en) * | 1981-10-22 | 1982-12-21 | Polaroid Corporation | Biphenyl aldehydes |
| US4638907A (en) * | 1984-11-28 | 1987-01-27 | The Procter & Gamble Company | Laminated laundry product |
| US5220074A (en) * | 1990-01-25 | 1993-06-15 | Daiso Co., Ltd. | Optically active isoxazole derivatives and intermediates for preparation thereof as well as processes for producing the same |
| US20040192972A1 (en) * | 2003-03-26 | 2004-09-30 | Council Of Scientific And Industrial Research | Process for the preparation of carbonyl compounds with a carbonyl group attached to the aromatic ring |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0620979B1 (en) * | 1993-02-09 | 1999-05-12 | The Quaker Oats Company | Process for preparing a low fat, transparent, stable oat protein containing aqueous solution and product thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3100796A (en) * | 1960-04-04 | 1963-08-13 | Dow Chemical Co | Method for making ar-poly(hydroxymethyl)diphenyl ethers |
| US3236898A (en) * | 1960-04-29 | 1966-02-22 | Polaroid Corp | 3-methyl-2, 5-dimethoxybenzaldehyde |
| US3322833A (en) * | 1963-01-24 | 1967-05-30 | Sun Oil Co | Preparation of aromatic aldehydes |
| US4108904A (en) * | 1976-09-22 | 1978-08-22 | American Cyanamid Company | Process for the preparation of m-phenoxybenzaldehyde |
| US4134925A (en) * | 1975-07-31 | 1979-01-16 | Dynamit Nobel Aktiengesellschaft | Ar-octahalogendiphenylether-4,4-dimethanols |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4085147A (en) * | 1976-02-05 | 1978-04-18 | Shell Oil Company | Preparation of meta-aryloxy-benzaldehydes |
| DE2620254C2 (en) * | 1976-05-07 | 1984-03-15 | Bayer Ag, 5090 Leverkusen | Process for the production of hydroxybenzaldehydes |
-
1978
- 1978-11-18 DE DE19782850180 patent/DE2850180A1/en not_active Withdrawn
-
1979
- 1979-10-29 US US06/089,010 patent/US4275241A/en not_active Expired - Lifetime
- 1979-11-05 DE DE7979104308T patent/DE2960541D1/en not_active Expired
- 1979-11-05 EP EP79104308A patent/EP0011208B1/en not_active Expired
- 1979-11-14 BR BR7907402A patent/BR7907402A/en unknown
- 1979-11-14 DD DD79216895A patent/DD147354A5/en unknown
- 1979-11-15 IL IL58732A patent/IL58732A/en unknown
- 1979-11-16 JP JP14789179A patent/JPS5572135A/en active Pending
- 1979-11-16 CS CS797863A patent/CS208795B2/en unknown
- 1979-11-16 DK DK488179A patent/DK488179A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3100796A (en) * | 1960-04-04 | 1963-08-13 | Dow Chemical Co | Method for making ar-poly(hydroxymethyl)diphenyl ethers |
| US3236898A (en) * | 1960-04-29 | 1966-02-22 | Polaroid Corp | 3-methyl-2, 5-dimethoxybenzaldehyde |
| US3322833A (en) * | 1963-01-24 | 1967-05-30 | Sun Oil Co | Preparation of aromatic aldehydes |
| US4134925A (en) * | 1975-07-31 | 1979-01-16 | Dynamit Nobel Aktiengesellschaft | Ar-octahalogendiphenylether-4,4-dimethanols |
| US4108904A (en) * | 1976-09-22 | 1978-08-22 | American Cyanamid Company | Process for the preparation of m-phenoxybenzaldehyde |
Non-Patent Citations (3)
| Title |
|---|
| Halasz, Soc. Chem. France, Bull. [5] 8, 1941, pp. 170-172, 175-176, 183-185. * |
| Houben-Weyl, Methoden der Organischen Chemie, George Thieme Verby, Struttgart, 1954, 7/1, pp. 171-174. * |
| Wiberg, Oxidation in Org. Chem. Part A, Academic Press, New York, 1965, pp. 145, 146, 151. * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4365072A (en) * | 1981-10-22 | 1982-12-21 | Polaroid Corporation | Biphenyl aldehydes |
| US4638907A (en) * | 1984-11-28 | 1987-01-27 | The Procter & Gamble Company | Laminated laundry product |
| US5220074A (en) * | 1990-01-25 | 1993-06-15 | Daiso Co., Ltd. | Optically active isoxazole derivatives and intermediates for preparation thereof as well as processes for producing the same |
| US20040192972A1 (en) * | 2003-03-26 | 2004-09-30 | Council Of Scientific And Industrial Research | Process for the preparation of carbonyl compounds with a carbonyl group attached to the aromatic ring |
| US6828463B2 (en) | 2003-03-26 | 2004-12-07 | Council Of Scientific And Industrial Research | Process for the preparation of carbonyl compounds with a carbonyl group attached to the aromatic ring |
Also Published As
| Publication number | Publication date |
|---|---|
| DD147354A5 (en) | 1981-04-01 |
| EP0011208B1 (en) | 1981-07-29 |
| DE2960541D1 (en) | 1981-10-29 |
| DK488179A (en) | 1980-05-19 |
| DE2850180A1 (en) | 1980-05-29 |
| EP0011208A1 (en) | 1980-05-28 |
| JPS5572135A (en) | 1980-05-30 |
| BR7907402A (en) | 1980-09-09 |
| CS208795B2 (en) | 1981-09-15 |
| IL58732A (en) | 1983-06-15 |
| IL58732A0 (en) | 1980-02-29 |
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